TWI483408B - Dye sensitized solar cell with glass powders and fabricating method thereof - Google Patents

Description

Dye-sensitized solar cell doped with glass powder and manufacturing method thereof

The present invention relates generally to solar cells, and more particularly to dye-sensitized solar cells incorporating glass frits and methods of making same.

Under the dual problems of energy depletion and environmental protection, solar energy is a green energy that is highly valued today. Therefore, the effective production of solar cells is a very broad research topic.

The solar cell is a device that directly converts solar energy into electrical energy. The earliest developed solar cell is a germanium-based solar cell developed by Bell Labs of the United States. Its main working principle is based on the photovoltaic effect of semiconductor. However, although the ruthenium-based solar cell has a high photoelectric conversion efficiency, its fabrication process is complicated, expensive, and the material specifications are quite demanding. Therefore, solar cells of various materials have been gradually developed.

A dye-sensitized solar cell (DSC) or a dye-sensitized solar cell is a solar cell of a nano-film material, which is formed by using a semiconductor nanocrystalline film formed on a conductive substrate. The surface adsorbs a photosensitizing dye, which in turn forms its working electrode. Dye-sensitized solar cells work by the fact that when the dye molecules absorb sunlight, their electrons transition to the excited state and are rapidly transferred to the semiconductor, while the holes remain in the dye. Thereafter, the electrons diffuse to the conductive substrate and are transferred to the counter electrode via the external circuit. Therefore, the dye in the oxidized state is reduced by the electrolyte, and the oxidized electrolyte receives electrons from the electrode and then returns Originally into the ground state.

Since dye-sensitized solar cells have advantages over germanium-based solar cells as follows: (1) easy process and low cost; (2) high power output at high temperatures, and high conversion efficiency in low light environments (3) The range of acceptable sunshine spectrum is large, and both sides of the template can absorb light, which is beneficial to absorb scattered light; (4) The incident light angle has less influence on the energy conversion rate; (5) Compared with other materials, there is no environmental pollution problem. . Therefore, in recent years, it has gradually become a hot research topic.

Currently, dye-sensitized solar cells use titanium dioxide (TiO2) as a semiconductor nanocrystalline film to adsorb a photosensitive dye as a light absorbing layer (also referred to as an active layer). In the process, the titanium dioxide slurry is first coated on the conductive substrate, and then fixed on the conductive substrate by high-temperature sintering. However, the formation of the titanium dioxide thin film layer on the conductive substrate by the current process method tends to cause peeling of the edge portion due to the low hardness, resulting in problems such as low stability of the dye-sensitized solar cell.

The object of the present invention is to solve the problem that the dye-sensitized solar cell is easy to be peeled off at the edge portion due to the low hardness of the light-absorbing layer of the dye and the titanium dioxide.

In order to achieve the above object, the present invention provides a dye-sensitized solar cell incorporating a glass powder, comprising: a first transparent substrate, a first electrode layer, a dye and titanium dioxide (the TiO2 light absorbing layer, an electrolyte layer, a second electrode layer, and a second transparent substrate, wherein the first electrode layer is disposed above the first transparent substrate, and the light absorption of the dye and the titanium dioxide The layer is disposed above the first electrode layer, and the light absorbing layer of the dye and titanium dioxide is doped with glass powder. The second electrode layer is disposed above the light absorbing layer of the dye and the titanium dioxide, and the second transparent substrate is disposed above the second electrode layer. Further, the electrolyte layer is disposed between the first electrode layer and the second electrode layer.

Furthermore, the present invention also provides a method for fabricating a dye-sensitized solar cell incorporating a glass powder, the method comprising: firstly, providing a first transparent substrate having a first electrode layer; and then providing a titanium dioxide slurry And coating a glass powder therein; and then coating the titanium dioxide slurry on the first electrode layer of the first transparent substrate; then, heating and sintering the titanium dioxide slurry to form a titanium dioxide film, and immersing the titanium dioxide film in the dye Forming a light absorbing layer of a dye and titanium dioxide; thereafter, providing a second transparent substrate having a second electrode layer; and placing the second transparent substrate over the light absorbing layer of the dye and the titanium dioxide, and making the second electrode The layer faces the light absorbing layer of the dye and the titanium dioxide; finally, an electrolyte is injected between the second electrode layer and the light absorbing layer of the dye and the titanium dioxide to form an electrolyte layer between the second electrode layer and the light absorbing layer of the dye and the titanium dioxide.

In some embodiments of the present invention, the method for preparing the titanium dioxide slurry comprises the steps of: firstly, adding titanium dioxide powder and glass powder to an absolute ethanol to form a first solution; then, adding terpineol ( Α-terprineol) is stirred in the first solution to form a second solution; thereafter, an ethylcellulose solution is provided in another absolute ethanol to form a third solution; then, the third solution is added to the second solution Forming a fourth solution; finally, removing the ethanol component in the fourth solution to form a titanium dioxide slurry.

In some embodiments of the invention, the weight ratio of the glass powder to the titanium dioxide powder is from 1% to 30%.

In some embodiments of the present invention, the glass powder is selected from the group consisting of a Bi ₂ O ₃ ‧B ₂ O ₃ composition, a SnO‧P ₂ O ₅ composition, a Bi ₂ O ₃ ‧ZnO composition, Bi ₂ O ₃ ‧B ₂ O ₃ ‧ZnO‧SiO ₂ composition, Bi ₂ O ₃ ‧B ₂ O ₃ ‧ZnO‧SiO ₂ ‧Al ₂ O ₃ composition, ZnO‧P ₂ O ₅ composition, or the above a combination of compositions.

In some embodiments of the invention, the step of heating the sintered titanium dioxide slurry to form a titanium dioxide film is heated to a softening point of the glass powder. In still other embodiments of the invention, the softening point is 550 ° C or less.

One aspect of the present invention is that when heating and sintering the titanium dioxide slurry, when heated to the softening point of the glass powder, the glass particles may collapse, and the effect of bonding the titanium oxide through the glass powder distributed in the titanium dioxide slurry may be Increase the hardness of the titanium dioxide film.

In some embodiments of the invention, the dye and the light absorbing layer of titanium dioxide have a pencil hardness H rating.

In summary, the present invention increases the hardness of the dye and titanium dioxide light absorbing layer by adding glass powder to the titanium dioxide slurry, and improves the stability of the dye-sensitized solar cell.

The detailed description below is intended to be illustrative of the embodiments of the present invention, and the accompanying drawings, Similarly, the graphic elements used herein The use of one or more "embodiments" is used to understand the particular architecture, structure or features described in at least one embodiment of the invention. Therefore, terms such as "in an embodiment" or "in another embodiment" are used to describe various embodiments and embodiments of the invention, and are not necessarily referring to the same embodiment. The examples should not be considered as mutually exclusive.

The embodiments and details that are described in detail below are illustrative of the drawings, which may be described in some or all of the embodiments below, as other potential embodiments or embodiments of the inventive concepts presented herein. . The detailed description of the embodiments of the present invention is provided as the following detailed description

In view of the fact that the dye-sensitized solar cell has a low hardness of the dye and titanium dioxide light-absorbing layer after the high-temperature sintering step, the edge of the dye-sensitized solar cell will be peeled off, which in turn affects the stability of the dye-sensitized solar cell (reliable degree). Therefore, one aspect of the present invention is that when the titanium dioxide slurry is heated to sinter to form a titanium dioxide film, when heated to the softening point of the glass powder, the glass particles collapse, and the glass powder distributed in the titanium dioxide slurry can be passed through. The effect of titanium dioxide bonding and thereby increasing the hardness.

Referring to Fig. 1, there is shown a schematic structural view of a dye-sensitized solar cell incorporating the glass powder of the present invention.

The structure of the dye-sensitized solar cell 100 includes: a first transparent substrate 101, a first electrode layer 103, a dye and a light-absorbing layer 105 of titanium dioxide, an electrolyte layer 107, a second electrode layer 109, and a First Two transparent substrates 111. In the present example, the first electrode layer 103 is disposed above the first transparent substrate 101, and the light absorbing layer 105 of the dye and titanium dioxide is disposed above the first electrode layer 103. Further, the second electrode layer 109 is disposed above the light absorbing layer 105 of the dye and the titanium dioxide, and the second transparent substrate 111 is disposed above the second electrode layer 109. Further, the electrolyte layer 107 is provided between the first electrode layer 103 and the second electrode layer 109.

The light absorbing layer 105 of the dye and the titanium dioxide includes titanium dioxide particles 1051, glass particles 1053, and dye particles 1055. The dye particles 1055 are photosensitive dyes which can be adsorbed on the titanium dioxide film to absorb light to achieve power generation. The titanium dioxide film synthesized by the glass particles 1053 and the titanium oxide particles 1051 is positioned above the first electrode layer 103, and is passed through the glass particles 1053 to adhere the titanium oxide particles 1051 to increase the hardness of the dye and the light absorbing layer 105 of the titanium dioxide.

Therefore, when light is incident from the front side of the first transparent substrate 101, the effect of electric power can be generated by the operation of the dye and the light absorbing layer 105 of the titanium oxide, the electrolyte layer 107, the first electrode layer 103, and the second electrode layer 107. In the embodiment, the first electrode layer 103 is an anode layer, and the second electrode layer 107 is a cathode layer.

Next, referring to Fig. 2, there is shown a flow chart showing a method for fabricating a dye-sensitized solar cell incorporating the glass powder of the present invention, together with the dye-sensitized solar cell incorporating the glass powder of the present invention shown in Fig. 1. The structure diagram is used for explanation.

First, a first transparent substrate 101 is provided, and a first electrode layer 103 is provided thereon (step 201).

In the embodiment, the first transparent substrate 101 used may be a glass substrate. However, it should be noted that it is readily known to those of ordinary skill in the art that any substrate that can achieve light transmission can be used as the first transparent substrate 101 without limitation.

In addition, in the embodiment, the first transparent substrate 101 has a first electrode layer 103. In other embodiments of the present invention, the first transparent substrate 101 may not have an electrode layer, and the first transparent layer is obtained. After the substrate 101, the first electrode layer 103 is formed over the first transparent substrate 101 without limitation.

In the embodiment, the first electrode layer 103 can be a transparent conductive layer to effectively achieve the effect of light transmission. The transparent conductive layer can be achieved by a transparent conductive oxide (TCO), for example, Indium Tin Oxide (ITO). Here, it should be noted that the first electrode layer 103 may also be formed of any transparent electrode material, and should not be limited.

Next, a titanium dioxide slurry is provided, comprising glass powder doped therein (step 203).

For the titanium dioxide slurry provided in the present embodiment, please refer to the flow chart of the method for preparing the titanium dioxide slurry of the present invention shown in FIG. 3, which is as follows: The titanium dioxide slurry is first prepared by adding titanium dioxide powder and glass powder to an absolute ethanol to form a first solution (step 301).

In the present embodiment, the titanium dioxide powder and the glass powder are added to the absolute ethanol in a predetermined weight ratio.

In some embodiments of the invention, the weight ratio of the glass powder to the titanium dioxide powder is from 1% to 30%. In the above, the preparation of 1% is taken as an example, and it is possible to prepare 1 gram of glass powder and 99 gram of titanium dioxide powder.

In some embodiments of the present invention, the glass powder may be selected from the group consisting of Bi ₂ O ₃ ‧B ₂ O ₃ composition, SnO‧P ₂ O ₅ composition, Bi ₂ O ₃ ‧ZnO composition , Bi ₂ O ₃ ‧B ₂ O ₃ ‧ZnO‧SiO ₂ composition, Bi ₂ O ₃ ‧B ₂ O ₃ ‧ZnO‧SiO ₂ ‧Al ₂ O ₃ composition, ZnO‧P ₂ O ₅ composition, or A combination of the above compositions.

However, it should be noted that the glass powder component described above is provided by way of reference only, and any glass powder component which can achieve the effect of the desired titanium dioxide particles of the present invention does not depart from the scope of the present invention, and should not be limit.

Moreover, in the present embodiment, after the first solution is formed, the first solution is placed in the ultrasonic oscillator and ultrasonically oscillated for about three hours.

Thereafter, terpineol (α-terprineol) is added to the first solution and stirred to form a second solution (step 303). In this step, the second solution is a solution in which terpineol is uniformly stirred with the first solution.

Next, an ethylcellulose solution is provided in another absolute ethanol to form a third solution (step 305). In this step, the third solution is required to completely dissolve ethylcellulose in absolute ethanol.

Further, a third solution is added to the second solution to form a fourth solution (step 307). In this step, the fourth solution is placed in an ultrasonic oscillator and subjected to ultrasonic oscillation for about one hour. Thereafter, stirring is continued.

Finally, the ethanol component in the fourth solution is removed to prepare a titanium dioxide slurry. (Step 309). In this step, the fourth solution is continuously stirred in step 307, and after overnight, the ethanol component in the fourth solution is removed by a rotary concentrator, and the mixture is mixed by a three-roll mill. Formed into a titanium dioxide slurry.

After the above steps of preparing the titanium dioxide slurry, the glass powder can be uniformly mixed in the titanium dioxide slurry.

Referring to the flowchart of the method for fabricating the dye-sensitized solar cell with glass powder shown in FIG. 2, after the titanium dioxide slurry is obtained, the titanium dioxide slurry is applied over the first electrode layer 103 (step 205). And, the sintered titanium oxide slurry is heated to form a titanium oxide film (step 207); thereafter, the titanium dioxide film is immersed in the dye to form a dye and titanium dioxide light absorbing layer 105 (step 209).

In the present embodiment, the titanium dioxide slurry is applied through a coating method to form a film over the first electrode layer 103, and the titanium dioxide slurry is fixed to the first electrode layer 101 of the first transparent substrate 101 by means of heat sintering. Above to form a titanium dioxide film. Wherein, the temperature of the heated and sintered titanium dioxide slurry is greater than the softening point of the glass powder, so that after heating, the glass powder distributed in the titanium dioxide slurry may collapse due to reaching the softening point thereof, so that the titanium dioxide slurry can be obtained. The titanium dioxide particles in the middle are pulled to increase the hardness of the titanium dioxide film.

In some embodiments of the present invention, the glass powder may have a softening point of about 550 ° C or less. Thus, when the titanium dioxide does not reach its softening point, it has reached the softening point of the glass powder.

In a particular embodiment of the invention, the system is heated to 500 ° C to reach Until the titanium dioxide is not softened, the glass powder has been collapsed.

The titanium oxide film formed on the first electrode layer 103 of the first transparent substrate 101 which is sintered at a high temperature is immersed in the dye so that the dye can be adsorbed in the titanium oxide film, and the light absorbing layer 105 of the dye and the titanium oxide is formed.

Here, it should be noted that the dye may be any of the existing photosensitizing dyes. For those having ordinary knowledge in the art, the dyes used may be changed according to actual needs, and therefore, any one of them may be used. The photosensitive dye to form the dye of the present invention and the light absorbing layer 105 of titanium dioxide are all encompassed within the scope of the present invention and should not be limited.

Next, a second transparent substrate 111 is provided, and a second electrode layer 109 is provided thereon (step 211).

In this embodiment, the second transparent substrate 111 may also be a glass substrate, and the second electrode layer 109 is a platinum (Pt) layer. Here, it should be noted that the material of the second transparent substrate 111 can be replaced by any material that can be used as a substrate, and should not be limited; and the second electrode layer 109 can also be applied to any of the cathode layers. Materials are substituted and should not be limited.

Thereafter, the second transparent substrate 111 is placed over the light absorbing layer 105 of the dye and titanium dioxide, and the second electrode layer 109 is faced to the light absorbing layer 105 of the dye and titanium dioxide (step 213). In this step, the second transparent substrate 111 is not directly in contact with the light absorbing layer 105 of the dye and the titanium dioxide. In some embodiments, the outer surface of the light absorbing layer of the dye and the titanium dioxide, that is, the first transparent substrate 101 and a barrier is disposed above the first electrode layer 103 A layer (not shown) is used to support the second transparent substrate 111 and leave a gap between the second electrode layer 109 and the light absorbing layer 105 of the dye and titanium dioxide.

Finally, an electrolyte is injected between the second electrode layer and the dye and titanium dioxide light absorbing layer to form an electrolyte layer 107 (step 215). In this step, a hole may be formed on the second transparent substrate 111, and the electrolyte is injected into the gap between the second electrode layer 109 and the dye and the titanium dioxide light absorbing layer 105 through the hole, when the electrolyte is the second electrode. When the gap between the layer 109 and the dye and the titanium dioxide light absorbing layer 105 is filled, the electrolyte layer 107 is formed.

In this embodiment, the electrolyte layer 107 of the lines I / I ₃ ^- is formed by the electrolyte.

Thus, the dye-sensitized solar cell incorporating the glass powder of the present invention can be produced by the steps of the production method shown in Figs. 2 and 3.

Next, please refer to the hardness comparison of the mixed layer of glass powder and dye without glass powder and titanium dioxide slurry as shown in Table 1 below:

It can be seen from Table 1 that the hardness of the dye layer of the undoped glass powder and the light absorption layer of titanium dioxide is B hardness, and the hardness of the mixed layer of the dye mixed with glass powder and titanium dioxide is increased to the pencil hardness H, Add glass powder to the titanium dioxide slurry, which can really make the dye and the second The hardness of the light absorbing layer of titanium oxide is increased.

Therefore, since the hardness of the light absorbing layer of the dye and the titanium oxide is increased, it is not easily peeled off from the first electrode layer (TCO) layer of the first transparent substrate (glass substrate), so that the stability of the dye-sensitized solar cell can be effectively improved. Degree (or reliability).

In summary, the present invention increases the hardness of the dye and titanium dioxide light absorbing layer by adding glass powder to the titanium dioxide slurry, and improves the stability of the dye-sensitized solar cell.

In addition, the various modifications that can be made by the embodiments and the embodiments described in the present invention are intended to be included within the scope of the present invention. Therefore, the drawings and the examples are intended to be illustrative and not to limit the invention, and the scope of the invention is intended to be limited only by the scope of the claims.

100‧‧‧Dye-sensitized solar cells

101‧‧‧First transparent substrate

103‧‧‧First electrode layer

105‧‧‧Dye and titanium dioxide light absorbing layer

1051‧‧‧ Titanium dioxide particles

1053‧‧‧ glass powder

1055‧‧‧Dye particles

107‧‧‧ electrolyte layer

109‧‧‧Second electrode layer

111‧‧‧Second transparent substrate

201~215‧‧‧Steps

301~309‧‧‧Steps

Fig. 1 is a schematic view showing the structure of a dye-sensitized solar cell incorporating a glass powder of the present invention.

Fig. 2 is a flow chart showing a method of producing a dye-sensitized solar cell incorporating the glass powder of the present invention.

Fig. 3 is a flow chart showing a method of producing the titanium dioxide slurry of the present invention.

100‧‧‧Dye-sensitized solar cells

101‧‧‧First transparent substrate

103‧‧‧First electrode layer

105‧‧‧Dye and titanium dioxide light absorbing layer

1051‧‧‧ Titanium dioxide particles

1053‧‧‧ glass powder

1055‧‧‧Dye particles

107‧‧‧ electrolyte layer

109‧‧‧Second electrode layer

111‧‧‧Second transparent substrate

Claims (8)

A dye-sensitized solar cell incorporating a glass powder comprises: a first transparent substrate; a first electrode layer disposed above the first transparent substrate; and a light absorbing layer of a dye and titanium dioxide (TiO ₂ ) Provided above the first electrode layer, wherein the dye and the light absorption layer of titanium dioxide are doped with a glass powder, and the glass powder has a softening point of 550 ° C or less, and after heating, to enhance the doping of the glass powder The hardness of the light absorbing layer; a second electrode layer disposed above the light absorbing layer of the dye and the titanium dioxide; a second transparent substrate disposed above the second electrode layer; and an electrolyte layer distributed over Between the first electrode layer and the second electrode layer. The dye-sensitized solar cell of claim 1, wherein the glass powder is selected from the group consisting of Bi ₂ O ₃ ‧B ₂ O ₃ composition, SnO‧P ₂ O ₅ composition, Bi ₂ O ₃ ‧ ZnO composition, Bi ₂ O ₃ ‧ B ₂ O ₃ ‧ ZnO ‧ SiO ₂ composition, Bi ₂ O ₃ ‧ B ₂ O ₃ ‧ ZnO ‧ SiO ₂ ‧ Al ₂ O ₃ composition, ZnO‧ P ₂ O ₅ composition, or a combination of the above compositions. The dye-sensitized solar cell of claim 1, wherein the weight ratio of the glass powder to the titanium dioxide is from 1% to 30%. The dye-sensitized solar cell of claim 1, wherein the dyeing The hardness of the mixed layer of the material and the titanium dioxide slurry is a pencil hardness H grade. A method for fabricating a dye-sensitized solar cell incorporating a glass powder, the method comprising: providing a first transparent substrate having a first electrode layer thereon; providing a titanium dioxide (TiO ₂ ) slurry, The titanium dioxide slurry comprises a glass powder doped therein; the titanium dioxide slurry is coated on the first electrode layer of the first transparent substrate; and the titanium dioxide slurry is heated to above the softening point of the glass powder to form a a high-hardness titanium dioxide film; the titanium dioxide film is immersed in the dye to form a dye and titanium dioxide light-absorbing layer; a second transparent substrate is provided, and the second transparent substrate has a second electrode layer thereon; the second transparent substrate And disposed on the light absorbing layer of the dye and the titanium dioxide, and the second electrode layer faces the light absorbing layer of the dye and the titanium dioxide; and an electrolyte is injected between the second electrode layer and the light absorbing layer of the dye and the titanium dioxide to form An electrolyte layer is between the first electrode layer and the second electrode layer. The method of claim 5, wherein the titanium dioxide slurry The preparation method comprises the steps of: providing titanium dioxide powder and glass powder into an absolute ethanol to form a first solution; adding terpineol (α-terprineol) to the first solution and stirring to form a second solution Providing an ethylcellulose solution in another absolute ethanol to form a third solution; adding the third solution to the second solution to form a fourth solution; and removing the ethanol component of the fourth solution The titanium dioxide slurry was prepared. The method of claim 6, wherein the weight ratio of the glass powder to the titanium dioxide powder is from 1% to 30%. The production method according to Item 6, wherein the glass powder is selected from the group consisting of Bi ₂ O ₃ ‧B ₂ O ₃ composition, SnO‧P ₂ O ₅ composition, Bi ₂ O ₃ ‧ZnO Composition, Bi ₂ O ₃ ‧B ₂ O ₃ ‧ZnO‧SiO ₂ composition, Bi ₂ O ₃ ‧B ₂ O ₃ ‧ZnO‧SiO ₂ ‧Al ₂ O ₃ composition, ZnO‧P ₂ O ₅ composition Or a combination of the above compositions.